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CN101660187A - Method for manufacturing submicron figure substrate based on preforming anode alumina - Google Patents

Method for manufacturing submicron figure substrate based on preforming anode alumina Download PDF

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Publication number
CN101660187A
CN101660187A CN200910192331A CN200910192331A CN101660187A CN 101660187 A CN101660187 A CN 101660187A CN 200910192331 A CN200910192331 A CN 200910192331A CN 200910192331 A CN200910192331 A CN 200910192331A CN 101660187 A CN101660187 A CN 101660187A
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aluminum
substrate
microsphere
manufacturing
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CN101660187B (en
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张佰君
黄智聪
王钢
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Sun Yat Sen University
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Sun Yat Sen University
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Abstract

本发明公开一种基于预成型阳极氧化铝的亚微米图形衬底制作方法,其包括以下步骤:在衬底上先镀上一铝层;在铝层表面均匀涂敷一微球结构层,并在微球表面蒸镀耐蚀性金属,蒸镀的耐蚀性金属将通过微球结构层间隙沉积在铝层表面,再将微球结构层去除;用稀酸进行腐蚀,在铝层上所蒸镀的金属之间形成凹坑,完成预成型的过程;利用浓酸将铝层上的耐蚀性金属去除;对铝层进行阳极氧化,形成具有预设孔洞结构图形的氧化铝层;利用氧化铝层作为掩模,通过刻蚀将氧化铝层上的孔洞结构图形转移到衬底上;去除氧化铝层,得到亚微米图形的衬底。本发明具有操作简单、快速、成本较低、孔径可控的优点。

Figure 200910192331

The invention discloses a method for manufacturing a submicron pattern substrate based on preformed anodized aluminum, which comprises the following steps: first coating an aluminum layer on the substrate; uniformly coating a microsphere structure layer on the surface of the aluminum layer, and Evaporate corrosion-resistant metal on the surface of microspheres, and the evaporated corrosion-resistant metal will be deposited on the surface of the aluminum layer through the gap of the microsphere structure layer, and then remove the microsphere structure layer; Pits are formed between the evaporated metals to complete the preforming process; the corrosion-resistant metal on the aluminum layer is removed by concentrated acid; the aluminum layer is anodized to form an aluminum oxide layer with a preset hole structure pattern; The aluminum oxide layer is used as a mask, and the hole structure pattern on the aluminum oxide layer is transferred to the substrate by etching; the aluminum oxide layer is removed to obtain a substrate with a submicron pattern. The invention has the advantages of simple and fast operation, low cost and controllable aperture.

Figure 200910192331

Description

Method for manufacturing submicron figure substrate based on preforming anode alumina
Technical field
The present invention relates to partly lead material growth field, relate in particular to a kind of method for manufacturing submicron figure substrate based on preforming anode alumina.
Background technology
The III-V group iii v compound semiconductor material is at photodiode, semiconductor laser, detector, and the electron device aspect has a wide range of applications.Solid state lighting is now popular topic, and gan (GaN) is a kind of important materials of solid state lighting, is exactly the core topic of solid state lighting and improve the light extraction efficiency.Wherein use graph substrate can effectively reduce between epitaxial film and the foreign substrate because the stress that lattice mismatch and thermal mismatching are brought gathers, improved the luminous efficiency of luminescent device.The graph substrate early stage of development,, generally adopt the figure of micron dimension owing to the restriction of Technology.Anodised aluminium (anodic aluminum oxide in recent years, AAO) technology constantly develops, can make the aperture is the following periodicity pore space structures of 500 nanometers, and is applied to by the mask lithography technology in the making of graph substrate, and the performance of luminescent device is effectively improved.
Traditional anodised aluminium is mainly realized by two step anodic oxidations.Because in the first step oxidation, hole produces randomly at alumina surface.This only causes the hole regularity of distribution of the aluminum oxide that obtains through oxidation step relatively poor.Adopt two step anodic oxidations can improve this situation.The first step oxidation is to form hole more clocklike on the aluminium surface.Earlier the zone of oxidation on aluminium surface is removed before the second step oxidation, that pitting clocklike will occur much on the aluminium surface, then carries out the second step oxidation.This step will form hole clocklike in whole zone of oxidation.
There are some shortcomings in the method that two-step oxidation is made anodised aluminium: one is exactly the more about several microns of size of hole, and the aperture is difficult to control; Second be exactly time of needing long.New technology is used in carries out pretreated method and has substituted for the first time that oxidation improves these shortcomings on the aluminium surface.One of them method is the array that carves the hexagon small salient point with beamwriter lithography on the single-crystal silicon carbide disk, is going out hexagonal pitting as mould at aluminium surface coining with this array.Through after the anodic oxidation, the position of these pittings will become hole.The big I of shape and size of the resulting hole of this a kind of method is determined by mould.The pretreated method that another control hole forms is exactly that elder generation carves pitting with focused ion beam (FIB) on the Al surface, forms anodised aluminium based on this.The preformed method of above-mentioned some, the technology cost is more expensive, is not suitable for large batch of industrialization growth.How adopting the cheap material and the graphic structure of prepared sub-micrometer scale, is a problem that the important application meaning is arranged.
Summary of the invention
At the shortcoming of prior art, the purpose of this invention is to provide a kind of simple to operate, quick, cost is lower, the method for manufacturing submicron figure substrate based on preforming anode alumina of controllable aperture.
For achieving the above object, technical scheme of the present invention is: a kind of method for manufacturing submicron figure substrate based on preforming anode alumina, and it may further comprise the steps: (1) plates an aluminium lamination earlier on substrate; (2) evenly apply a micro-sphere structure layer on the aluminium lamination surface, and in microsphere surface evaporation corrosion resistant metal, the corrosion resistant metal of evaporation will be deposited on the aluminium lamination surface by the micro-sphere structure lamellar spacing, the micro-sphere structure layer be removed again; (3) corrode with diluted acid, between the metal of institute's evaporation on the aluminium lamination, form pit, finish preformed process; (4) utilize concentrated acid that the corrosion resistant metal on the aluminium lamination is removed; (5) aluminium lamination is carried out anodic oxidation, form alumina layer with default pore space structure figure; (6) utilize alumina layer as mask, by etching with the pore space structure figure transfer on the alumina layer to substrate; (7) remove alumina layer, obtain the substrate of submicron figure.
Described substrate is sapphire, silicon, silicon carbide, gan, aluminium nitride, zinc oxide or gallium arsenide.
Described micro-sphere structure layer is made of polystyrene, silicon oxide or epoxy third lipoid microsphere.
Hole size is by the size decision of microballoon, by chemical process corrosion or plasma etching method control diameter of micro ball and size at interval.
By oxygen ICP etching micro-sphere structure layer, change diameter of micro ball, the size of regulating microballoon.
In the step (5), place polyprotonic acid feeding certain voltage to carry out oxidation substrate and aluminium lamination, polyprotonic acid is 5% phosphoric acid, 10% sulfuric acid or 5% oxalic acid, and its corresponding voltage is 100V~130V, 25~27V or 30~50V.
In the step (2), be coated with one deck photoresist material on the aluminium lamination surface earlier, again the spin coating of micro-sphere structure layer mixing water got on, afterwards its heating is dried,, when removing the micro-sphere structure layer photoresist material is removed simultaneously so that the micro-sphere structure layer is attached on the photoresist material.
In the step (2), described corrosion resistant metal is gold, nickel, chromium or tin.
In the step (5), periodically the aperture of pore space structure changes by the method for the diameter of regulating polystyrene microsphere, anodised time, acid strength, and the pore space structure degree of depth was regulated by the anodised time.
In the step (6), the figure of anodic oxidation rear oxidation aluminium lamination is a pore space structure periodically, its by wet chemical or dry plasma etch with figure transfer to substrate.
Compared with prior art, the present invention has following advantage:
The present invention's fabrication cycle or acyclic figure.Utilize the method for anodised aluminium fabrication techniques graphic structure with respect to other, this method is through a preliminary shaping and an anode aluminaization submicron figure to be transferred on the semiconductor epitaxial material, has simple to operate, quick, cost is lower, advantages such as controllable aperture.
Description of drawings
Fig. 1~7th, the whole process flow side schematic view of making sapphire graphical substrate among the embodiment 1
About accompanying drawing, 1 represents substrate among the figure, and 2 represent aluminium lamination, and 3 represent the micro-sphere structure layer, and 4 represent the corrosion resistant metal layer, and 5 representatives are through anodic oxidation rear oxidation aluminium.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in detail.
Embodiment 1
Referring to Fig. 7, be the epitaxially grown graph substrate side schematic view that can be used for of final molding.Wherein comprise Sapphire Substrate 1.Wherein Sapphire Substrate can change other substrates into, and as silicon (Si), silicon carbide (SiC), gan (GaN), aluminium nitride (AlN), zinc oxide (ZnO), gallium arsenide (GaAs) substrate, or other are used for the substrate material of nitride material growth.
With the Sapphire Substrate is example, and the preparation method of graph substrate shown in Figure 1 may further comprise the steps:
A, elder generation are with Sapphire Substrate chemical solution and pure water, and ultrasonic cleaning is clean.On substrate 1, plate the aluminium lamination 2 of 2~5 μ m.Then its phosphoric acid with 5% was polished 5 minutes down at 5 ℃, voltage is 100V, as shown in Figure 1.
B, microballoon and ethanol are hybridly prepared into mixing solutions, and mixing solutions is spin-coated on the aluminium lamination surface.Polystyrene microsphere will be gathered into unit molecule micro-sphere structure layer, as shown in Figure 2.Described micro-sphere structure layer is made of polystyrene, silicon oxide or epoxy third lipoid microsphere.Present embodiment adopts polystyrene microsphere.
C, deposit corrosion resistant metal on the micro-sphere structure layer, described corrosion resistant metal is gold, nickel, chromium or tin, and present embodiment adopts the nickel metal, and its thickness is 10nm.Because exist the gap between the microballoon, the pairing substrate in gap will deposit last layer nickel, as shown in Figure 3.Then substrate, aluminium lamination and micro-sphere structure layer are immersed in the DI water, the micro-sphere structure layer are separated with aluminium lamination by the method for ultrasonic vibration.And clean with organic solvent and pure water ultrasonic cleaning, as shown in Figure 4.
D, substrate and the aluminium lamination that has a metal are immersed in 10% dilute sulphuric acid the inside 2 minutes because nickel has solidity to corrosion to dilute sulphuric acid aluminium easily with the dilute sulphuric acid reaction, so there is not that a part of aluminium of nickel protection to be gone down the formation pit by corrosion fast.Will form default pore space structure like this, can be designed to periodically or acyclic pore space structure, as shown in Figure 5 according to actual needs.
E, sample carry out oxidation 2~10 hour at 5%, 100 ℃ of phosphoric acid under with the voltage of 100V through cleaning the back.After oxidation, can obtain tens alumina layers, as shown in Figure 6 to the hundreds of nanometer.This step can prolong or the minimizing time as required, and obtains the different hole diameter and the degree of depth.
F, utilize this formable layer anodised aluminium as mask, on ICP,, the periodic pattern on the anodised aluminium is transferred on the substrate with Ar gas plasma etching, so just on substrate, obtain periodically pore space structure, as shown in Figure 7.
G, erode the anodised aluminium mask layer.
H, sample are clean with ultrasonic cleaning.
To this step, just can obtain having the periodically substrate of pore space structure, as Fig. 7.Grown epitaxial layer in the above.
Embodiment 2
Similar to embodiment 1, because introduce nickel preformed the time as mask being Al,, can between steps d, e, add the step of removing nickel in order to eliminate the influence that nickel may be introduced in subsequent step.Rafifinal passivation can occur at the sulfuric acid of concentration more than 80%, has solidity to corrosion, and nickel does not then have solidity to corrosion.Utilize above said characteristic, nickel can be removed, and less to the influence of aluminium.
Specific implementation method is: the steps d in embodiment 1, e add following steps between the step:
Sample is immersed at normal temperatures in 98% the vitriol oil 10~30 minutes.The concrete time is according to the thickness decision of nickel dam.
Embodiment 3
Directly polystyrene microsphere and alcoholic acid mixing solutions are spin-coated on the surface of Al, the bonding strength that might occur between microballoon and the Al is not enough, and causes the microballoon position problem that moves to occur.In order to address this is that, can be coated with one deck photoresist material on the Al surface earlier, again the spin coating of microballoon mixing water is got on.This step can not be used organic solution, and organic solution can be influential to photoresist material.Afterwards its heating is dried, microballoon will be attached on the photoresist material.With acetone or glue-dispenser photoresist material and microballoon are together removed at last.
Specific implementation method is to carry out following steps after step a:
A, apply the photoresist material of 600nm after will sample cleaning in the above, the thickness of photoresist material does not need very high, mainly be requirement entire sample surface-coated evenly.Sample is placed on the hot plate with 100 ℃ of heating 30 seconds, and purpose is only to make the photoresist material surface cure.
B, polystyrene microsphere and water are hybridly prepared into mixing solutions, and mixing solutions is spin-coated on the photoresist material surface.Polystyrene microsphere will be gathered into the unimolecular layer structure.Sample is being placed on the hot plate with 100 ℃ of heating 2 minutes.Microballoon will some imbed the photoresist material the inside like this, and this just reaches the fixedly purpose of microballoon.
C, sample is being used the oxygen etching on ICP.That a part of photoresist material that does not have microballoon to stop so can be etched into.The oxygen etching be requirement will not be blocked the part photoresist material all remove, until the Al layer till.
D, the nickel of 10nm on the evaporation in the above, that is nickel on the position that does not have photoresist material will deposit.
E, photoresist material is removed with acetone or glue-dispenser.Microballoon also can be along with photoresist material removes together.Use organic solvent and pure water ultrasonic cleaning clean at last.Till this step, just can obtain the sample that step c obtains among the embodiment 1.
F, following step just can be carried out according to steps d~g among the embodiment 1.
Embodiment 4
Because the size of microballoon is that standard, fixed are arranged, so the aperture in hole, hole just can not be regulated arbitrarily.Can after applying polystyrene microsphere, promptly behind the step b of embodiment 1,, diameter of micro ball be diminished, regulate the size of microballoon with oxygen ICP etching.To realize to hole and adjusting at interval.Then carry out step c again.

Claims (10)

1、一种基于预成型阳极氧化铝的亚微米图形衬底制作方法,其特征在于包括以下步骤:1. A method for manufacturing a submicron pattern substrate based on preformed anodized aluminum, characterized in that it comprises the following steps: (1)在衬底上先镀上一铝层;(1) An aluminum layer is first plated on the substrate; (2)在铝层表面均匀涂敷一微球结构层,并在微球表面蒸镀耐蚀性金属,蒸镀的耐蚀性金属将通过微球结构层间隙沉积在铝层表面,再将微球结构层去除;(2) Evenly coat a microsphere structure layer on the surface of the aluminum layer, and vapor-deposit corrosion-resistant metal on the surface of the microsphere, the corrosion-resistant metal evaporated will be deposited on the surface of the aluminum layer through the gap of the microsphere structure layer, and then Microsphere structure layer removal; (3)用稀酸进行腐蚀,在铝层上所蒸镀的金属之间形成凹坑,完成预成型的过程;(3) corroding with dilute acid, forming pits between the evaporated metals on the aluminum layer, and completing the preforming process; (4)利用浓酸将铝层上的耐蚀性金属去除;(4) Utilize concentrated acid to remove the corrosion-resistant metal on the aluminum layer; (5)对铝层进行阳极氧化,形成具有预设孔洞结构图形的氧化铝层;(5) Anodizing the aluminum layer to form an aluminum oxide layer with a preset hole structure pattern; (6)利用氧化铝层作为掩模,通过刻蚀将氧化铝层上的孔洞结构图形转移到衬底上;(6) Using the aluminum oxide layer as a mask, the hole structure pattern on the aluminum oxide layer is transferred to the substrate by etching; (7)去除氧化铝层,得到亚微米图形的衬底。(7) Removing the aluminum oxide layer to obtain a substrate with submicron patterns. 2、根据权利要求1所述的制作方法,其特征在于:所述衬底为蓝宝石、硅、碳化硅、氮化镓、氮化铝、氧化锌或砷化镓。2. The manufacturing method according to claim 1, wherein the substrate is sapphire, silicon, silicon carbide, gallium nitride, aluminum nitride, zinc oxide or gallium arsenide. 3、根据权利要求1所述的制作方法,其特征在于:所述微球结构层由聚苯乙烯、氧化硅或环氧丙脂微球构成。3. The manufacturing method according to claim 1, wherein the microsphere structure layer is composed of polystyrene, silicon oxide or glycidol microspheres. 4、根据权利要求3所述的制作方法,其特征在于:孔洞大小由微球的尺寸决定,通过化学方法腐蚀或等离子刻蚀方法控制微球的直径及间隔的大小。4. The manufacturing method according to claim 3, characterized in that the size of the holes is determined by the size of the microspheres, and the diameter and spacing of the microspheres are controlled by chemical etching or plasma etching. 5、根据权利要求3所述的制作方法,其特征在于:通过氧气ICP刻蚀微球结构层,改变微球的直径,来调节微球的尺寸。5. The manufacturing method according to claim 3, characterized in that the microsphere structure layer is etched by oxygen ICP to change the diameter of the microsphere to adjust the size of the microsphere. 6、根据权利要求5所述的制作方法,其特征在于:步骤(5)中,将衬底及铝层置于多元酸中通入一定电压进行氧化,多元酸为5%磷酸、10%硫酸或5%草酸,其对应电压为100V~130V、25~27V或30~50V。6. The production method according to claim 5, characterized in that: in step (5), the substrate and the aluminum layer are placed in a polybasic acid and passed through a certain voltage for oxidation, and the polybasic acid is 5% phosphoric acid, 10% sulfuric acid Or 5% oxalic acid, the corresponding voltage is 100V-130V, 25-27V or 30-50V. 7、根据权利要求1至6任一项所述的制作方法,其特征在于:步骤(2)中,先在铝层表面涂一层光刻胶,再将微球结构层混合水旋涂上去,之后对其加热烤干,以使微球结构层黏附在光刻胶上,去除微球结构层时将光刻胶同时去除。7. The production method according to any one of claims 1 to 6, characterized in that: in step (2), first coat a layer of photoresist on the surface of the aluminum layer, and then spin-coat the microsphere structure layer mixed with water , and then heat and dry it, so that the microsphere structure layer adheres to the photoresist, and the photoresist is removed at the same time when the microsphere structure layer is removed. 8、根据权利要求1所述的制作方法,其特征在于:步骤(2)中,所述耐蚀性金属为金、镍、铬或锡。8. The manufacturing method according to claim 1, characterized in that in step (2), the corrosion-resistant metal is gold, nickel, chromium or tin. 9、根据权利要求1所述的制作方法,其特征在于:步骤(5)中,周期性孔洞结构的孔径通过调节聚苯乙烯微球的直径、阳极氧化的时间、酸液浓度的方法来改变,孔洞结构深度通过阳极氧化的时间来调节。9. The production method according to claim 1, characterized in that: in step (5), the pore diameter of the periodic pore structure is changed by adjusting the diameter of polystyrene microspheres, the time of anodic oxidation, and the concentration of acid solution , the depth of the pore structure is adjusted by the time of anodizing. 10、根据权利要求1所述的制作方法,其特征在于:步骤(6)中,阳极氧化后氧化铝层的图形为周期性孔洞结构,其通过化学湿法或等离子干法刻蚀将图形转移到衬底上。10. The manufacturing method according to claim 1, characterized in that: in step (6), the pattern of the aluminum oxide layer after anodic oxidation is a periodic hole structure, and the pattern is transferred by chemical wet or plasma dry etching onto the substrate.
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CN110997988A (en) * 2017-07-18 2020-04-10 Imec 非营利协会 The valve metal layer is transformed into a template comprising a plurality of spaced (nano) channels and forming therein a spacer structure
CN108342683A (en) * 2018-02-09 2018-07-31 京东方科技集团股份有限公司 A kind of pre-sputtering substrate and preparation method thereof
CN109504994A (en) * 2018-12-13 2019-03-22 上海科技大学 A kind of preparation method of Novel anode alumina formwork and nano-array
CN109504994B (en) * 2018-12-13 2020-08-21 上海科技大学 A new type of anodic aluminum oxide template and preparation method of nano-array
CN110703365A (en) * 2019-10-18 2020-01-17 浙江水晶光电科技股份有限公司 Optical lens and preparation method thereof

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